Condensation products of



Patented Aug. 17, 1937 CONDENSATION PRODUCTS OF 2.3-HY- DROXYNAPHTHOIC ACID Wolfgang Winkelmiiller,

Leverkusen-Wiesdorf,

Germany, assignor to GeneralAniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application November 7,

Serial No. 48,777. In Germany November 14,

4 Claims. (c1. 200-32 The present invention relates to condensation products of 2.3-hydroxynaphthoic acid bearing in the naphthalene nucleus substituents which do' not cause solubility in water with anthranilic acid amide or its substitution products, more particularly it relates to compounds which may be represented by the following formula:

wherein the naphthalene nucleus bears substit- I I I OH b t'tu t-- 0H su s 1 en l NH 2 substituent- 6 V HzN' HzN ooo11+ H2N\ (II) p '30 o OH . substituentfiggl I r 35 s uents which do not cause solubility in water, such as alkyl, alkoxy, halogen, the nitro group and the like, and wherein I My new compounds of the above-identified formula are obtainable by reacting upon a substitution product of 2.3-hydroxynaphthoic acid bearing in the naphthalene nucleus at least one substituent which does not cause solubility in Water with anthranilic acid amide or a suitable nuclear substitution product thereof in the presence of a dehydrating agent. Advantageously the process is carriedout in two steps by first 10 reacting upon the nuclear substituted 2.3-hydroxynaphthoic acid chloride with anthranilic acid amide or a substitution product thereof respectively, whereby the corresponding 2.3-hydroxynaphthoyl-anthranilic acid amide is obl5 tained, and then performing the ring closure. The process can be illustrated by the followingscheme:

The ring closure from 111 to II very easily enters and can be performed, for example, by heating the substance sub III at or above its melting, point respectively, or by heating the same in 45 a suitable neutral agent, suchas glycerine, or in apotassium-sodium-acetate melt. It can already be performed at low-temperature if a condensing agent is added, for example, when working in boiling amylalcohol in the presence of go potassium acetate or when introducing the compound into a sodium-chloride-aluminium-chloride melt. Most practically the ring closure is performed by heating and dissolving the sub- 5 stance sub III in aqueous caustic alkali lye. On

cooling, the alkali metal salt of the new compound indicated above sub II which is diflicultly soluble in excess alkali separates; it easily can be isolated, and with the aid of acids the free compound can be obtained. Or otherwise the free compound can be obtained by introducing carbon-dioxide into the hot alkaline solution whereby the free compound is precipitated.

It has already been known that the benzoylhaving the formula:

NHC OCs 5 yields the corresponding condensation product a by splitting off water "(see Korner; Journal fiir praktische Chemie, N. F. vol. 36, page 155) however, from this, the chemical behaviour of 'the 2.3ehydroxynaphthoyl-anthranilic acid amides could not be foreseen, it rather couldbe expected that the hydroxy group in 'o position would influence the proceeding of the reaction. 3 First of all it'could not be expected that the new condensation products would have thevaluable properties of the 2.3-hydroxynaphthoic acid arylamides and therefore would be important intermediate products for the manufacture ofdyestuffs of good fastness properties.

' The' invention'is illustrated by the following examples, without being limited thereto, the parts being by weight:

1 Example, 1 40 21.8 parts of 6-m.eth0xy-2.3-hydroxynaphthoic acid, parts of toluene and 11.9 parts of thionylchloride are heated at 90-100 C. with the exclusion of moisture until a clear solution has formed andthe development of hydrochloric acid has ceased. The solution of the 6-methoXy-2.3 hydroxynaphthoic acid chloride obtained is: added in portions while. stirring. to a warm solution.

of 13.6 parts of anthranilic acid amide in 300 parts of toluene, and the reaction mixture is reflux-ed until hydrochloric acid does no longer escape. Thereby the fi-methoxy-zfi-hydroxyey naphthoyl anthranilic acid amide separates in form of a greenish yellow somewhat resinous intermediate (after recrystallizing from nitro'- benzene decomposing at 232 C.) By dissolving the reaction product in an aqueous caustic soda lye of 4% and heating the ring closure is performed and the condensation product having the following formula:

is precipitated as a greyish green. powder by in? troducing carbon dioxide:(point of decomposi tionabove300 0.). v

In an analogous manner there have beenpre pared the condensation, products from anthra nilic acid amide and 'I-rnethbxy-ZB-hjrdroxy- (and also the acetyl) anthranilic acid amide naphthoi acid (point of decomposition above 300 C.) 6-methyl-2.3-hydroxynaphthoic acid (point of decomposition above 300 C.) fi-bromo- 2.3-hydroxynaphthoic acid (point of decomposition above 300 C.), found by analysis 21.2%

of bromine, calculated 21.8% of 'bromine; 7-

chloro-2.3-hydroxynaphthoic acid (point of decomposition above 360 0.), found by analysis 8.5% of nitrogen, 11.2% of chlorine, calculated 1 8.7% of nitrogen, 11.0% of ,chlorine, Further in an analogous manner there have been prepared the condensation products from Z-amino- 4z-methoxybenzamide and 6 methoxy-2.3 hydroxynaphthoic acid (point of decomposition above 300 C.) from 4-methyl-2-aminobenzamide and 7methoxy+2.3-hydroxynaphthoic acid (point of decomposition above 300 C.).

' Example 2 Into a suspension of 23.2 parts of 8-nitro-2.3- hydroxyn'aphthoic ac'id and 13.6 parts of anthranilic acid amide inabout 250 parts of toluene there are dropped while stirring 10 parts of phosphorus trichloride dissolved in 30 parts of toluene. The reaction mass is heated to boiling, while further stirring until the development of hydrochloric acid has ceased, whereby the reaction product having the following formula:

wherein the naphthalene nucleus bears at least I one substituent selected from the group consisting of alkyl, alkoxy, halogen and the nitro group, and wherein stands for a member selected from the group consisting of a benzene nucleus and an allgvl-, a1koxy-., halogenzene nucleus, being generally yellowish crystalline substances soluble-in alkalies and being val i uable intermediate products for the manufacture of dyestuffs.

a a and nitro-substituted' ben- 2. The compound of the following formula:

being a yellowish crystalline substance soluble in alkalies and being a valuable intermediate product for the manufacture of dyestufis. 15 3. The compound of the following formula:

being a yellowish crystalline substance soluble in alkalies and being a valuable intermediate prodnot for the manufacture of dyestuffs.

4. 2.3-hydroxynaphthoic acid derivatives of the formula:

WOLFGANG WINKELMULLER. 

